Viscose spinning solutions



Patented Dec. 9, 1947 VISCOSE SPINNING SOLUTIONS Rudolph S. Bley, Milligan College, Tenn, assignor to North American Rayon Corporation, New York, N. Y., a corporation of Delaware No Drawing.

Original application October 7,

1938, Serial No. 233,824. Divided and this application December 30, 1943, Serial No. 516,240

4 Claims.

In the manufacture of cellulosic products, such as filaments, and the like, a viscose solution is continuously extruded through the minute orifices.of a spinneret into a coagulating bath (setting bath). However, since the introduction of the viscose process great troubles have been and are still experienced as far as continuous spinning is concerned due to impurities, such as, for example, precipitated cellulose particles, sulphur and resin particles, zinc compounds, etc., present in either the viscose solution or the spin bath. These impurities gradually contaminate the spinnerets, clog and reduce the widths of the spinneret orifices with the result that filaments of uneven thickness are obtained. If contamination proceeds the individual filaments start to tear and occasion interruption of the spinning process.

I have found that contamination of spinnerets and clogging of spinneret holes (orifices) may be substantially overcome by spinning viscose solutions in the presence of cation-active substances or acid addition products thereof having the general structure:

in which R represents an aliphatic acyl radical having 8 or more carbon atoms, R1 represents a hydrogen atom or an acyl, alkyl, aryl or aralkyl radical, R2, R3 and R4 represent alkyl and/or aryl and/or aralkyl radicals, n is a whole number, and X represents an innocuous anion.

Cation-active compounds are surface-activecompounds which carry in the cation a hydrocarbon chain having 8 or more carbon atoms. They are particularly advantageous because they may be used in neutral salt, alkaline and acidic aqueous solutions, and also in hard water. In contradistinction to cation-active compounds, anion-active compounds are surface-active compounds Which carry in the anion a more or less extended hydrocarbon chain. They flocculate in neutral salt, alkaline and acidic aqueous solutions, and also in hard water. Common soaps, sulphonated oils, etc., are anion-active compounds, and thus they are unable to prevent the incrustation of spinnerets and spinneret orifices.

Incrustation inhibitors, in accordance with the present invention, may be prepared by causing high-molecular, mono-acylated or unsymmetrical diacylated alkylenediamines with alkylating, arylating or aralkylating agents, such as dimethyl sulphate, methyl iodide, methyl bromide,

phenyl bromide, p-toluene-ethyl sulphonate, etc.

The acetylated or acylated alkylenediamines may be prepared in accordance with processes set forth in U. S. Patent No. 1,534,525.

Although these cation-active incrustation inhibitors may form corresponding bases in viscose solutions and salts in acid spin baths, they retain their surface-activity and, thus, their property of substantially preventing incrustations on prolonged spinning. If very small amounts of these cation-active compounds are added to viscose solutions or spin baths the physical characteristics, such as strength, plasticity, lustre, etc., of regenerated cellulose produced therefrom or therein, respectively, remain unaltered. Upon increasing the amount of incrustation inhibitor in a given viscose solution or spin bath, the regenerated cellulose produced therefrom or therein, respectively, may alter its physical characteristics, i. e., it may acquire a soft-lustre, become more plastic, lose part of its original strength etc. For such reasons, the amounts to be added to viscose solutions and/or spin baths must be predetermined by experimentation. Additions of about 0.1 to 5.0 grams per liter of viscose solution or spin bath are generally sufiicient to allow continuous spinning without substantially affecting the inherent physical characteristics of regenerated cellulose threads, films, etc. Although these cation-active incrustation inhibitors improve the spinning of any conventional viscose solution or spin bath, I have found that they are especially valuable as additions to zinc-bearing spin baths, 1'. e., spin bathscontaining a soluble zinc compound, for example; zinc sulphate, these baths, having poor spinning qualities. I am well aware that cation-active alkylene diamines have, heretofore, been prepared as wetting agents. However, the prior art does not disclose the use of these derivatives as incrustation inhibitors, the object of the present invention.

Example I About 380 parts of oleyl-diethyl-ethylene-die amine are reacted with about 126 parts of dimethylsulphate, About 0.3 to 2.0 grams of the oily mono oleyl diethyl-methylethylene-diammonium-methyl-sulphate are added to about one liter of a viscose solution of conventional cellulose content and maturity. This solution is then extruded through a spinneret into a conventional spin bath, such as, for example, a glucose bath, a magnesium zinc bath, etc. The spinnerets and their princes remain clean on prolonged spinning.

3 Other cation-active alkylenediamine derivatives having the general structure set forth above may be used with equal success.

Example II About 382 parts of stearyl-diethyl-ethylene diamine are melted and reacted with about 126 parts of dimethyl sulphate. The soapy mass is probably mono-stearyl-diethyl-methylethylenediammonium-methyl-sulphate.

A conventional viscose solution is extruded through fine orifices of precious metal spinnerets into an acid spin bath, containing for example, sulphuric acid, sodium sulphate, ammonium sulphate and zinc sulphate and about 0.3 to 5.0 grams per liter of mono-stearyl-diethyl-methylethylene diammonium-methyl-sulphate, Spinning difiiculties and irregularities are substantially overcome. Without the addition of an incrustation inhibitor spinning is'interrupted after a very short period of time. This inhibitor may be replaced by similar derivatives obtained from 1auryl-diethylenediamine, octancyl-diethylenediamine, lauryl-dipropylenediamine, octanoyl-di propylenediamine, etc.

Example III 360 parts of oleyl-diethylethylene-diamine are reacted with about 142 parts of benzyl chloride. The resulting oily product, probably mono-oleyldiethyl-benzylethylene-diammonium-chloride, is added to both the viscose solution and the spin bath. The formation of zinc rings and sulphur craters is substantially overcome.

Although these examples will serve to illustrate the present invention. I do not wish to be limited to the incrustation inhibitors and concentrations thereof recited therein, since I may make use of any cation-active alkylene derivative and acid addition products thereof having the structure:

in which R represents an aliphatic acyl radical having 8 or more carbon atoms, R1 represents a hydrogen atom or an acyl, alkyl, aryl or aralkyl radical, R2, R3 and R4 represent alkyl and/or aryl and/or aralkyl radicals, n is a whole num* her, and X represents an innocuous anion, provided' it is sufiiciently soluble and stable in spin baths and/or viscose solutions to furnish surfaceactive cations therein. Modifications of my invention will readily be recognized by those skilled in the art, and I desire to include all such modifications coming within the scope of the appended claims.

This is a division of my copending application, Ser. No. 233,824, filed October 7, 1938, Patent No. 2,345,570, entitled Coagulating bath containing cation-active inhibitors.

I claim:

1. A viscose spinning so ution containing a dissolved, substantially stable, cation-active alkylene derivative having the structure:

in which R represents an aliphatic acyl radical having 8 or more carbon atoms, R1 represents a substituent selected from the group consisting of hydrogen, acyl radicals, alkyl radicals, aryl radicals and aralkyl radicals, R2, R3 and R4 represent alkyl radicals, n is a whole number and X represents an innocuous anion.

3. A viscose spinning solution containing a dissolved, substantially stable, cation-active alkylene derivativehaving the structure:

in which R represents an aliphatic acyl radical having 8 or more carbon atoms, R1 represents a substituent selected from the group consisting of hydrogen, acyl radicals, alkyl radicals, aryl radicals and aralkyl radicals, R2, R3 and R4 represent aryl radicals, n is a whole number and X represents an innocuous anion.

4'. A viscose spinning solution containing a dissolved, substantially stable, cation active alkylene derivative having the structure:

m lb

in which R represents an aliphatic acyl radical having 8 or more carbon atoms, R1 represents a substituent selected from the group consisting of hydrogen, acyl radicals, alkyl radicals, aryl radicals and aralkyl radicals, R2, R3 and R4 represent aralkyl radicals, n is a whole number and X represents an innocuous anion.

RUDOLPH S. BLEY.

REFERENCES CITED The following references are of record in thc file of this patent:

UNITED STATES PATENTS Number Name Date 2,345,570 Bley Apr. 4, 1944 2,125,031 Polak et, a1. July 26, 1938 2,310,208 Bley Feb. 9, 1943 2,310,207 Bley Feb. 9, 1943 2,294,379 Bley Sept. 1, 1942 2,294,378 Bley Sept. 1, 1942 2,132,930 Bley Oct. 11, 1938 

